Water-soluble pyrimidine dyes



United States Patent 3,418,308 WATER-SOLUBLE PYRIMIDINE DYES Hans Ischer and Hans Siegrist, Basel, Switzerland, as-

signors to Sandoz Ltd. (also known as Sandoz AG), Basel, Switzerland No Drawing. Continuation-impart of application Ser. No. 109,009, May 10, 1961. This application Nov. 13, 1963, Ser. No. 323,272

M 3,418,308 Ice Patented Dec. 24, 1968 R represents hydrogen, chlorine, bronnne, methyl, car- Claims priority, application Switzerland, Apr. 27, 1961,

6 boxy or carboxymethyl, 17 Claims Cl. 260-154) hal represents a halogen atom with an atomic number from 17 to 35, inclusive, i.e. chlorine or bromine,

n represents one of the integers 1 and 2, and

m represents one of the integers 1 and 2.

ABSTRACT OF THE DISCLOSURE l5 Water-soluble pyrimidine dyes of good fastness prop- Process the Pmductlon of the new dyes erties on animal fibers, synthetic polyamide fibers, celluprises (a) reacting dyes of the formula losic fibers, etc. correspond to the formula hal wherein the several variables have the meanings set forth With a halopyfimidille 0f e f la in the disclosure proper. The characteristic and deterhal mining feature is the positioning of the --CH O- pyrimi- I dine radical on the middle component. 0

I? C-R3 The present application is a continuation-in-part of our hal o\ CAM application Ser. No. 109,009; filed on May 10, 1961 (now N abandoned).

The invention relates to water-soluble pyrimidine dyes of the formula Q m-l or (b) condensing a compound of the formula D -Q hal h l D N/ \C R3 3 N N 2 i ll C C hal wherein D is the radical of a monoazo dye hearing from 1 to 3 sulfonic acid groups, eg of the benzene-azo-naph- R1 thalene, naphthalene-azo-naphthalene or benzene-azo- I S-pyrazolone series, of a l-amino-4- arylamino-anthra- HzN /C -hal quinone-Z-sulfonic acid, -2,5-, -2,6-, -2,7- or -2,8-disulionic acid dye or of a copper-phthalocyanine dye, CH20- I H hearing from 2 to 3 sulfonic acid groups or from 1 to li k 0-1131 2 sulfonic acid groups and from 1 to 2 sulfonic acid N amide groups,

D2 i a 1 i 0-a 'flq i 1I 0 C a i a or (c) condensing an intermediate which is capable of which is bound to in the Position 4 and y dye formation and bears a -SO -hal or -CO-hal hear an additional sulfonic acid group in one of the group with an ami f th f l positions 5, 6, 7 and 8,

D is the radical of a coupling component bearing from 31 R 1 to 3 sulfonic acid groups of the hydroxy-naphthalene, aminonaphthalene, 1-phenyl-3-methyl-S-pyrazolone, 1- naphthyl-3 methyl 5 pyrazolone, acetoacetylaminobenzene, acetoacetylaminonaphthalene or phenylazowith an amine of the formula wherein X represents hydrogen or the radical of the formula I C\ hal t W -C C-hal Formula IV with a coupling component bearing 1 to 3 sulfonic acid groups.

The process according to (a) is applicable in principle with all known classes of dyes, especially the series of anthraquinone, phthalocyaniue and azo dyes, of which the monoazo and disazo dyes as a rule give particularly interesting results. The dyes, especially the phthalocyamine and azo dyes, may contain metal atoms bound by coordination links, for example chromium, cobalt, nickel or copper atoms, or metallizable groupings, the latter being converted into the corresponding metal complexes in substance or on the fiber by the known methods.

The second mode of operation (b) of the process consists in reacting amines of Formula IV with organic dyes contain at least one CO-hal or SO -hal group. Suitable dyes of this type are e.g. azo, anthraquinone and phthalocyanine dyes containing the aforecited groups.

For example, azo dyes may be used which contain at least two sulfonic acid chloride groups of which one is reacted with an amine of Formula TV while the other or others are saponified to sulfonic acid groups, care being taken that the reactive group is not damaged. Suitable anthraquinone dyes are e.g. l-amino-2-sulfo-4-arylaminoanthraquinones which bear one or two sulfonic acid chloride groups in the arylamino nucleus. The phthalocyanine dyes contain preferably three or four sulfonic acid chloride groups e.g. copper phthalocyanine-trior -tetrasulfonic acid chloride.

In place of dyes containing at least one CO-hal or 4O -hal group, organic compounds (procedure can "be employed which contain at least one CO-hal or SO -ha1 group and in addition at least one substitituent which permits dye formation. An example of such a substituent rendering the compound capable of dye formation is the amino group which can be formed by saponification of an acylamino group or by reduction of a nitro group and subsequent diazotization, upon which the resulting diazonium compound is coupled. Generally, the substituent can be one which is reacted by the standard methods of dye chemistry so that from the preliminary product a dye is formed. At least one of the components forming the dye must contain the number of water-solubilizing groups necessary to impart watersolubility on the dye, notable examples being carboxylic and sulfonic acid groups and sulfonic acid amide groups.

The condensation of the amines (IV) with the named dyes or with the compounds convertible into dyes is conducted preferably in aqueous medium. But is can also be carried out in organic solvents or in mixtures of organic solvents and water, these media being particularly advantageous in the case of poorly water-soluble or water-insoluble intermediate products. Suitable organic solvents are alcohols, acetone, benzene, toluene, chlorobenzene and tertiary organic bases such as pyridine.

The condensation temperature is adjusted to the reactivity of the individual starting products and varies within wide limits. The preferred temperature range is 0 to C. but somewhat higher temperatures can also be employed.

According to the procedure ((1) an amine of Formula IV is diazotized and coupled with a water-soluble coupling component; the known and commonly used methods are employed, the preferred coupling conditions being a temperature of 020 0, especially 0-10" 0., and

a weakly acid, neutral or weakly alkaline medium.

Examples of suitable coupling components are:

l- 2'-chloro-5 '-sulfo phenyl-3-methyl-5-pyrazolone,

1-(3'-sulfo)- or 1-(4-sulfo)-phenyl-3-methyl-5-pyrazolone,

1-(2'.5'-disu1fo)- or 1-(2.4-disulfo)-phenyl-3-methyl- S-pyrazolone,

1-(4"-acetylarnino-2'.2"-disulfo-l.1-stilbenyl-4')- 3-methyl-5-pyrazolone,

1-(2.5-dichloro-4'-sulfo)-phenyl-3-methyl-5-pyrazolone,

2-hydroxynaphthalene-4-, -6-, -7- or -8-sulfonic acid,

2-hydroxynaphthalene-3.6- or -6.8-disulfonic acid or -3.'6. 8-trisulfonic acid,

1- 2'-hydroxy -ethoxy-8-hydroxynaphthalene- 3.6-disulf0nic acid,

1-hydroxynaphthalene-4- or -5-sulfonic acid,

1-hydroXynaphthalene-3.6- or -4.6-disulfonic acid or -3.6.8-trisulfonic acid,

6-chloro-2-hydroxynaphthalene-4-sulfonic acid,

1- 4-chloro) -benzoylamino-S-hydroxynaphthalene- 3.6-disulfonic acid,

. 1- (4-methyl)-phenylsulfonylamino 8-hydroxynaphthalene-3.6-disulfonic acid,

l-acetylaminoor 1-propionylamino8-hydroxynaphthalene-2.4-, -3.6- or -4.6-disulfonic acid,

1-benzoylamino-8-hydroxynaphthalene-2.4-, -3.6- or -4.6-disulfonic acid,

l-acetylaminoor 1-propionyla'mino-8-hydroxynaphthalene-4-sulfonic acid,

2- or 3-acetylamino-, -propionylaminoor S-hydroxynaphthalene-7-sulfonic acid, 2-acetylaminoor 2-benzoylamino-8 hydroxynaphthalene- 3.6-disulfonic acid, 1-acetoacetylaminobenzene-3- or -4-sulfonic acid, -2.4- or -2.5-disulfonic acid, 1-acetoacetylamino-Z-methylor -2-rnethoxyor -2-chloro-benzene-S-sulfonic acid, 1-acetoacetylamino-4-methylor -4-chlorobenzene- 2-sulfonic acid, 1-acet0acetylamino-Z.4-dimethylbenzene-6-sulfonic acid, 1-acetoacetylaminonaphthalene-4-, -5-, -6-, -7- or -8-sulfonic acid, -3.6-, -3.8- or -4.8-disulfonic acid or -3.6.8-trisulfonic acid, Z-acetoacetylaminonaphthalene-S- or -6-sulfonic acid, -3.6-, -4.8-, -5.7- or -6.8-disulfonic acid or -3.6.8- or -4.6.8-

trisulfonic acid.

-benzoylamino- The amines of Formula IV are prepared by reacting halopyrimidines of Formula III with amines of the formula CHz-OH (VII) Suitable amines of this type are e.g. 3-amino-4- or -6-me thoxyor -ethoxybenzyl alcohol, 3-amino-2-, -4- or -6-methylbenzyl alcohol, 3-amino-4- or -6-hydroxy-benzyl alcohol, 3-amino-4- or -6-chloroor -4-cyanobenzyl alcohol, 3-amino-4-butoxybenzyl alcohol, 3-amino-4.5- diethoXy-benzyl alcohol, 3-amino-5-bromo 6 hydroxybenzyl alcohol, 3-amino-2-methyl-5-chlorobenzyl alcohol, 3-arnino-4-methyl-5-cl11orobenzyl alcohol and above all S-aminobenzyl alcohol itself.

The reaction of the amines of Formula VII or of the intermediates or of the water-soluble dyes bearing a CH OH group with the halopyrimidines of the Formula III is carried out preferably in aqueous medium, but it can also be carried out in organic solvents or in mixtures of organic solvents and water, which can be of especial advantage for the reaction of poorly watersoluble or water-insoluble intermediate products. Suitable organic solvents are alcohols, acetone, benzene, toluene, chlorobenzene, and tertiary organic bases such as pyridine etc. The halopyrimidines can be used as such in concentrated form or in solution in an organic solvent. Acetone, benzene, chlorobenzene and toluene are specially suitable solvents for the halopyrimidines.

The reaction temperature is adjusted to the reactivity of the individual starting products. The prefered temperature range is 0 to C., but higher temperatures up to about 30 C. can be used.

The reaction is carried out in an alkaline medium, preferably in a strongly alkaline medium. To neutralize the hydrogen halide formed, an acid-binding agent e.g. sodium or potassium carbonate, trisodium phosphate, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide is added to the reaction solution in solid, pulverized form or as an aqueous solution either at the start of or during the reaction. The addition of small amounts of a wetting or emulsifying agent to the reaction mixture can accelerate the rate of reaction.

The final pyrimidine dye is salted out of its solution or suspension (which if desired may be previously neutralized) with sodium or potassium chloride or precipitated with acid, and is then filtered with suction, washed, neutralized and dried. The amines of Formula IV and the intermediates which bear a group of the formula (VIII) are in general poorly soluble in water and can be isolated by filtration, if necessary, after precipitation by means of salts, or they can be directly employed for the conversion into water-soluble dyes, e.g. by diazotizing the amines of Formula IV. If the reaction with the halopyrimidines of Formula III has been carried out in organic medium the reaction products are isolated by one of the fundamental operations such as direct filtration, evaporation of the solvent and filtration, precipitation by means of a suitable agent and filtration etc.

The new Water-soluble pyrimidine dyes are suitable for dyeing leather, for dyeing, padding and printing fibers of vegetable and animal origin such as cotton, linen, hemp, ramie, jute, wool, silk, fibers of regenerated cellulose such as viscose staple fiber and filament yarn, casein fibers, animalized cellulosic fibers, synthetic polyamide fibers e.g. nylon, Perlon, Rilsan (registered trademarks) and mixtures of the aforenamed fibers. The dyes with 1 or 2 sulfonic acid groups are rather suitable for the acid dyeing of wool, silk and synthetic polyamide fibers and for the dyeing of cellulosic fibers by the exhaustion process, whereas the better soluble dyes with 2 or more sulfonic acid groups can be used for the printing and the pad-dyeing of cellulosic fibers. The new dyes are applicable by semiand full-continuous dyeing techniques such as the pad-jig Pad-Roll (registered trademark), pad-steam, pad-batch and thermal fixation process. They are also suitable for dyeing viscose (cellulose xanthate) in the spinning solution, the spun-dyed shades thus obtained have very good light and wet fastness.

The optimum trial conditions for the application of the dyes vary very considerably according to the nature of the fiber. For the dyeing, padding or printing of animal fibers and synthetic polyamide fibers it is preferable to use an acid, neutral or weakly alkaline medium for the application or fixation of the dyes, containing, for example, acetic acid, formic acid, sulfuric acid, ammonium sulfate, lactic acid, oxalic acid, sodium acetate, sodium bicarbonate, sodium or potassium carbonate, sodium metaphosphate, trimethylamine, pyridine, quinoline etc. The dyes can also be applied from acetic acid to neutral medium in presence of levelling agents, e.g. polyoxethylated fatty amines or mixtures of these and alkylpolyglycol ethers, and the bath adjusted to a neutral or weakly alkaline reaction at the end of dyeing by the addition of small amounts of an agent of alkaline reaction, e.g. ammonia, sodium bicarbonate or carbonate etc. or compounds which react alkaline on heating, e.g. hexamethylene tetramine, urea. Following this, the goods are thoroughly rinsed and if necessary acidified with a little acetic acid.

The dyeings and prints on animal fibers and synthetic polyamide fibers possess good fastness to light, washing, milling, perspiration, water, rubbing and dry cleaning. Owing to the formation of a chemical linkage between the dye molecule and the fiber molecule the fixed dyeings and prints also can withstand a treatment with boiling 1:1 pyridine-water mixture.

The dyeing, padding and printing of cellulosic fibers is carried out in alkaline medium, e.g. in presence of sodium bicarbonate, sodium or potassium carbonate, sodium or potassium hydroxide solution, calcium hydroxide, sodium metasilicate, sodium borate, water glass, trisodium phosphate, ammonia, etc. To prevent reduction reactions during dyeing, padding or printing the addition of a mild oxidizing agent, e.g. sodium 1-nitrobenzene-3- sulfonate, is often of advantage. The fixation of the dyes in dyeing, padding and printing can be carried out simultaneously with or subsequent to application, in the same bath or in a fresh bath, if necessary after intermediate drying. If a fresh bath is used it is advisable to carry out fixation in presence of water-soluble salts, e.g. sodium chloride or sulfate, in order to avoid a partial redissolving of the dye in the bath. The fixation of the dye radical on the fiber can be carried out by heating e.g. by steaming at l00104 C., by dry heating at temperatures from 120 to 200 C., by conditioning at C. and at constant humidity, by treating at 80l00 C. in an alkaline solution containing per liter 200-300 grams of sodium chloride or sodium sulfate. However, by using sufficiently strong alkalis such as sodium or potassium hydroxide, triosodium phosphate, sodium metasilicate, and in some cases even sodium carbonate, it is also possible to fix the dyes at temperatures of about 20- 40 C. and preferably at room temperature (about 25 C.). The addition of certain quaternizable amines such as trimethylamine or triethylene diamine, or of the asymmetrical dimethylhydrazine, preferably in stoichiometric amounts, accelerates the fixation of the dye on the fiber so that the fixation temperature can be lowered and/ or the fixation time shortened and/or the alkalinity or the amount of alkali reduced. The fixation results in the formation of a stable chemical linkage between the dye molecule and the fiber molecule to which are due the outstanding wet fastness properties of the dyeings and prints. The fixation yield is in most cases excellent, but a small amount of the dye applied generally does not take part in the reaction with the fiber and this unreacted portion is removed by suitable treatments such as washing and/ or soaping, if necessary at higher temperatures. For this purpose synthetic detergents can be employed, e.g. alkylarylsulfonates, such as sodium dodecylbenzenesulfonate, alkyl sulfates such as sodium lauryl, cetyl or oleyl sulfate, optionally sulfated or carboxymethylated alkylpolyglycol ethers or optionally sulfated or carboxymethylated monoand dialkylphenylpolyglycol ethers.

The dyeings on cellulosic fibers possess good fastness to light, washing, milling, water, perspiration, alkali, rub bing and dry cleaning.

In comparison with the known dyes which bear a halopyrimidylamino group of the formula N (IX) the new dyes of the Formula I possess a considerably higher fixation rate on cellulosic fibers, so that their fixation is completed in a small fraction of the time required for the fixation of the dyes bearing a halopyrimidyl-amino group of the Formula IX.

In contrast to the dyes of the formula wherein E is the radical of a water-soluble coupling component, e.g. a hydroxynaphthalene-disulfonic acid, which rreact slowly with cellulosic fibers, the next comparable dyes of the formula Example 1 47.9 parts of the dye (as sodium salt) produced by coupling diazotized 3-aminobenzyl alcohol with 1-(2'.5'- dichloro) phenyl 3 methyl 5 pyrazolone 4' sulfonic acid are dissolved in 670 parts of water. The solution is cooled to 8-10 and brought to a pH value of 11-12 by adding a sodium hydroxide solution. In the course of 2 hours 20 parts of 2.4.6-trichloropyrimidine are added in small portions with vigorous stirring, and

stirring continued at 8-10 for 10-20 hours until condensation is completed. During this time the pH value is maintained at 11-12 by dropping in a sodium hydroxide solution. The dye formed is filtered off, washed with a solution of common salt and dried. It is a water-soluble yellow powder which dyes wool, silk and cellulosic fibers in brilliant, greenish-yellow shades with very good fastness to light and wet treatments.

By replacing the parts of 2.4.6-trichloropyrimidine by the equivalent amount of 2.4.6-tribromoor 2.4.5.6- tetrachloroor 2.4.5 .6-tetrabromopyrimidine, similar dyes are obtained.

A solution of 0.2 part of the above-described dye in parts of water is stirred into 235 parts of a viscose solution of 8.5% tat-cellulose content. After stirring for minutes at 2025 and about 150 r.p.m. the colored spinning solution is placed in an refrigerator and left for about 10 hours to allow the entrapped air bubbles to escape. The de-aerated viscose solution is then spun in the normal manner. The filaments are washed in a solution of an anionic detergent at and then in several fresh baths of water at 50. They are then treated in a deacidifying bath, e.g. a solution of 0.3% sodium carbonate and 0.2% sodium bicarbonate, for 1 hour at 80 85, then in a solution of an anionic detergent at 50 and once again in several baths of water at 50. The filaments 8 are then dried. They are dyed to a greenish yellow shade of very good fastness to light, washing, water, perspiration, rubbing and dry cleaning.

Example 2 12.3 parts of 3-aminobenzyl alcohol are dissolved in 150 parts of water and then 42 parts of 30% sodium hydroxide solution are added. The solution is cooled to 2 with ice, and during 3 hours a solution of 18.3 parts of 2.4.6-trichloropyrimidine in 22 parts of toluene is added dropwise with stirring, the temperature being maintained at 03. Subsequently, stirring is continued for 10-15 hours at 03 and then 35.5 parts of 30% hydrochloric acid are added. After another hour the solution is filtered off, the residue washed with a common salt solution dried at 3540 with vacuum.

13.5 parts of the 3-amino-l-(dichloropyrimidyloxymethyl)-benzene thus obtained are added to 170 parts of water, 14.7 parts of 30% hydrochloric acid and a small amount of an emulsifying agent. Diazotization is carried out at l5-20 by the addition of a solution of 3.5 parts of sodium nitrite in 10 parts of water, with vigorous stirring. Stirring is continued for a further 60 minutes at this temperature and then insoluble impurities are filtered off. The clear diazo solution is slowly added to a solution, cooled to 5, or 17.3 parts of sodium 1-(2'.5-dichloro)- phenyl-3-methyl-5-pyrazolone-4-sulfonate and 10 parts of sodium bicarbonate in 300 parts of water. To complete coupling stirring is continued for a further 10 hours at this temperature and the pH value subsequently brought to 2-3 by the addition of hydrochloric acid. The dye formed is filtered off and dried at about with vacuum. It is a yellow, water-soluble powder and identical with the dye of Example 1. 2 parts of the dried dye are dissolved in 4000 parts of water and the solution heated to 40. 2 parts of acetic acid are added and 100 parts of a wool fabric are entered into this bath, which is brought to the boil within 15-20 minutes and maintained at the 'boil for 45-60 minutes. After cooling to 90, 3 parts of 25% ammonia or 3 parts of hexamethylene tetramine are added and the bath maintained at for 20 minutes. The fabric is rinsed thoroughly, acetic acid being added to one of the rinsings, and subsequently dried. A level, greenish yellow dyeing of good fastness to washing, perspiration, milling and light is obtained.

18.9 parts of sodium 1-phenyl-3-methyl-5- y.razolone- 2.4'-disulfonate or 18.9 parts of sodium 1-phenyl-3-methyl-5-prazolone-2'.5'-disulfonate may be used as coupling component in place of 17.3 parts of sodium 1-(2'.5'-dichloro) phenyl 3 methyl 5 pyrazolone 4' sulfonate to give yellow dyes which owing to their better solubility in water are also well suitable for the printing or the pad-dyeing of cellulosic fibers.

The 2.4.6-trichloropyrimidine used in the first paragraph of this example can be replaced by the equivalent amount of 5-bromo-2.4.6-trichloroor 2.4.5 .6-tetrachloropyrimidine. The final dyes obtained possess also excellent fastness to light and wet treatments.

Example 3 13.5 parts of 3-amino-l-(dichloropyrimidyloxymethyl)-benzene are diazotized according to the particulars of Example 2. The diazo solution is run with stirring into a solution, cooled to 24, or 23.4 parts of sodium l-benzoylamino 8 hydroxynaphthalene 3.6 disulfonate and 15 parts of sodium bicarbonate in 450 parts of water. Stirring is continued for a further 2 hours at 24, the precipitated dye filtered off and washed with a common salt solution. After drying with vacuum, a red powder is obtained which dissolves in water with a red coloration.

Example 4 13.5 parts of 3-amino-l-(dichloropyrimidyloxyrnethyl)-benzene are diazotized according to the particulars of Example 2. The diazo solution is run into a neutral so- Parts Dye obtained as described above 30 Urea 200 Water 305 Sodium alginate thickening (4%) 450 Sodium carbonate 15 The print is dried, steamed for 5-10 minutes at about 102, rinsed thoroughly with cold water, soaped at the boil for minutes, rinsed again with water and dried. A

brilliant orange-red print is obtained which has very good wet and light fastness.

Example 5 13.5 parts of 3-amino-1-(dichloropyrimidyloxymethyl)- benzene are diazotized according to the particulars given in Example 2. The diazo solution is run into a solution, cooled to 0-2, of 17.4 parts of sodium l-hydroxynaphthalene-4.6-disulfonate and 10.5 parts of sodium bicarbonate in 200 parts of water. Ice is added at the same time to maintain the temperature constant at 02, and the solution stirred overnight at this temperature. The precipitated dye is filtered off with suction, washed with common salt solution and dried with vacuum. A red powder is obtained which dissolves in water with a scarlet colora tion.

The same dye is also obtained by condensing 48.2 parts of the dye sodium 1-hydroxy-2-(3-hydroxymethyl-phenylazo)-naphthalene-4.6-disulfonate with 18.5 parts of 2.4.6- trichloropyrimidine according to the details given in Example 1.

A mercerized cotton fabric is impregnated at room temperature with a freshly prepared padding solution containing 15 parts of the above dye, 150 parts of anhydrous sodium sulfate, parts of sodium metasilicate and 13.5 parts of 30% sodium hydroxide solution in 1000 parts of water. The fabric is then squeezed to contain 80% of its weight of moisture and rolled up. The roll is wrapped in airtight material e.g. a sheet of polyethylene, and slowly rotated or stored for 4 hours at room temperature. It is then rinsed in cold and hot water, soaped at the boil for 15 minutes with a solution containing 0.5 g./l. of an anionic or a non-ionic detergent, e.g. an alkylpolyglycol or an alkylarylpolyglycol ether which may be sulfated or carboxymethylated and rinsed again. A brilliant scarlet dyeing, is obtained which is very fast to light and to wet treatments. The obtained dyeing is more than 3 times stronger than the corresponding dyeing produced with the condensation product of 2.4.6-trichloropyrimidine and sodium 1 hydroxy-2-(3'-aminophenylazo)-naphthalene- 4.6-disulfonate.

A piece of mercerized cotton fabric is impregnated at room temperature on the pad with an aqueous solution containing 15 grams of the above dye per liter, squeezed so that the pick-up of liquor is about 70% and dried at room temperature and 65% relative humidity. The fixation is carried out for 60 minutes at in a fixation bath containing 300 grams of anhydrous sodium sulfate and 5 grams of anhydrous sodium carbonate per liter. The fixed dyeing is rinsed with hot water and then with cold water, soaped for 15 minutes at the boil with a solution of 1 gram of soap per liter of distilled water, rinsed again and dried. The obtained scarlet dyeing is fast to light and to wet treatments and is about 3 times stronger than the corresponding dyeing produced with the condensation product of 2.4.6-trichloropyrimidine and sodium 1-hydroxy-2-(4- hydroxymethyl-phenylazo) naphthalene-4.6disulfonate. By carrying out the fixation at or by replacing the sodium carbonate by 2 ml. of 30% sodium hydroxide solution and working at 25 or at 90 the fixation rate is considerably increased but the ratio of the fixation yields remains about 3:1.

Example 6 49.6 parts of the dye (as the disodium salt) produced by coupling diazotized 3-amino-4-methyl-1-hydroxymethyl-benzene with 1-hydroxynaphthalene-4.6-disulfonic acid, are dissolved in 300* parts of water. 15 parts of 30% sodium hydroxide solution are added to this solution, which is cooled to 02. In the course of 30 minutes it is run at this temperature into a vigorously stirred suspension containing 19 parts of 2.4.6-trichloropyrimidine and a small amount of an emulsifying agent in parts of water at 02.

On completion of condensation, the excess sodium hydroxide is neutralized with hydrochloric acid and the suspension diluted with 1000 parts of water and brought to a temperature of 50. The dye is then precipitated with common salt, filtered off and dried. It is obtained a red powder which dissolves in water with a red coloration.

A cotton fabric is padded at room temperature with a padding liquor consisting of 30 parts of the above dye, 15 parts of calcined sodium carbonate and 150 parts of urea in 800 parts of water, using a pad with two or more bowls giving an expression (pick-up) of about 75%. It is then dried, preferably to a moisture content of about 10%. Condensation is carried out at -150 for 6 minutes, the fabric rinsed in cold and hot water, soaped at the boil and finally rinsed.

A red dyeing very fast to Wet treatments and to light is obtained.

Example 7 A mixture consisting of 20 parts of 2.4.6-trichloropyrimidine and 100 parts of water is stirred vigorously at 0-2 with an emulsifier until an emulsion is formed. Then a solution of 8 parts of sodium hydroxide and 51.7 parts of the dye (as the disodium salt) produced by coupling diazotized 3 amino 4 chloro 1 hydroxymethylbenzene with l-hydroxynaphthalene-4.6-disulfonic acid in 320 parts of water is run in, the temperature being maintained at 02 by external cooling.

On completion of condensation the reaction mixture is neutralized with hydrochloric acid, diluted to 2 liters with water and heated to 60. Water-insoluble byproducts are filtered off, and the dye formed precipitated with sodium chloride, filtered off and dried with reduced pressure at 5060.

The dye is obtained as a red powder which gives brilliant red shades of very good light and wet fastness when applied by the dyeing or printing processes described in Examples 2, 4 and 5.

The 3-amino-4-chloro-l-hydroxymethylbenzene used as diazo component can be produced from 2-chloro-1-nitrobenzene by reacting it with symmetrical dichlorodimethyl ether, subsequently hydrolysing the chloromethyl group and reducing the nitro group. A similar dye is produced if the 2.4.6-trichloropyrimidine is replaced by an equivalent amount of 2.4.6-tribromo-, 2,4,5,6-tetrachloroor 2.4.5.S-tetrabromopyrimidine.

The following Table 1 contains further dyes of the formula which are produced according to the details of Examples 1 to 7 and are characterized by the substituents of the nucleus A, the symbols D and Z and the shade of the pad-dyeings on cotton or of the dyeings on wool.

TABLE 1 Substituents of A Shade of the Paddyeings on Co tton No. of Posi- Substit- Posi- Substit- Z equals radical oi- D3 equals radical of or of the Dyelngs Example tion uent tion uent on Wool I) (V II) 8 2.41.5.6-tetrachloropyrimL l-acctoacetylaminobenzene-2.4-disulfonic acid Yellow.

me. 9 -dn l-acegoacetylaminonaphthalene-3.6-disulfonic Do.

aci 1O 2.4.6-trichloro-5-methyll-acetoacetylaminonaphthalene-4-sulfonic acid Do.

pyrimidine. 6 Chlorine 2.4.6-trich1oro-5-carboxyl-acetoacetylamino-Z.5-dichlorobenzene-4-sul- Do.

methylpyrimidine. ionic ac 6 Cyano 2.4.6-trichloropyrimidine.- I-(Z naphthyI)-3-methyl-5-pyrazolone-5.7-di- Do.

sulfonic acid. 6 Methoxy--. dn .fl do Do. 6 Ethoxy- 1-phenyl-3-methyl-5-pyrazolone-2.5-d sulfonic Do. 6 Butoxy do 1-phe1yl-3-methyl-5-pyrazolone-2.4 -d1sulion1c Do.

aci 5 Ethoxy. 6 Ethoxy do do Do. 4 MethyL l-hydroxynaphthalenei.6-dis11lf0nic acid Scarlet. 6 do go 2 hydroxynaphthaJene-fi.8-disulf0nic acid Orange. 0. o o.

4 Hydroxy" Bromine- .do 2-hydroxynaphthalene-3.6.8-trisulfonic acid. Red. 2 Methyl... 5 Chlorine. do do Red. 6 Hydroxy do 2-hydroxynaphthalene-4-sn]fonic acid Orange 6 do 2.4.6-trichloro-5-carboxy- 2-l1ydroxynaphthalene-8-sulfonic acid Do.

mcthylpyrimidine. 24 .do 2-hydroxynaphthalene-6sulfonic acid Do. 25 2 Methyl 5 Chlorine" 2.4.6-trichloropyrimidinel-aceiylanaino-S-hydroxynaphthalene-Z.4-disnl- Bluish red.

onic aci 26 2 do 5 do 2.4.6tribromopyrirnidine 2-acegoacetylaminonaphtha1cne-3.6.8-trisu1fonic Yellow.

aci 27 4 Hydroxy 2.4.6-trichloro-5-ca1'boxypy- 1-pr0pionylamino-8-hydroxynaphtha1ene-3.6-di- Bluish red.

rimidine. sulfonic acid. 2 Methyl 2.4.6-trichloro-5-methylpy- Z-hydroxynaphtha1ene-6.8-disulfonic acid Orange.

mm me. do do.-. 1-naphthyl-(2)-3-mcthyl-5-pyraz010ne-4.8-di- Yellow.

sulfonic acid. do do Do.

2.4.6-trichloropyrimidine. 1-hydroxynaphthalene-3,ddisulfonic acid. Orange-red. 0 l-hydroxynaphthalene-4,8-disulfonic acid Scarlet. 2,4,5,6-tetrachloropyl-acetylamino-8-hydroxynaphthalene-3,6-di- Bluish red.

riniidine. sulfonic acid. 34 do l-pl einyl-3-methyl-5-pyrazo10ne-2,4-disu1ionic Grecm'sh yellow.

ac1 35 4 Methoxy 2.4.fi-trichloropyrimidine-- l-phenyl-3-rnethy1-5-pyrazol0ne-3-sulfonic acid Yellow. 36 4 Ethoxy do 1-(4-acetylamino-1.1-stilbenyl4'-)-3-methyl- Do.

5-pyrazolone-2.2-disu1tonic acid. 37 4 Chlorine do 1-(2-hydroxy)-ethoxy-8-hydroxynaphthalene- Scarlet red.

3.6-disulfonic acid 38 5 do 6 Methyl do l-acetylamino-8-hydroxynaphthalene4.6-di- Bluish red.

sulfonic acid. 39 do 1-acetylarnino-8-hydroxynaphthalene-i-sul- Do.

ionic acid. 40 do l-propionylaminc-8-hydroxynaphthalene-4- Do.

sulfonic acid. 41 d n l-benzoylamino-8-hydroxynaphthalene-46 Do.

disulfonic acid. 42 6 Methyl l-hydroxynaphthalene-3,6,8-trisulfonic acid Red. 43 6 do do 2-hydroxynaphthalene-3,6-disuli0nic acid Red. 44 do l-bcnzoylamino-S-hydroxynaphthalene2.4- Bluish red.

disulionic acid. 45 dn l-propionylamino-S-hydroxynaphtha1ene46- Do.

disnlfonic acid. 46 2.4.6-trichloropyrimidinel-hydroxynaphthalene-3-sulfonic acid Scarlet. 47 do l-hydroxynaphthalenel-sulfonic acid. Do. 48 do l-hydroxynaphthalene-Mulfonic acid Do. 49 .do 2-hydroxynaphthalene-7-sulfonic acid Orange. 50 do 1-(4-chloro)-benzoylaminl-8 hydroxyn Bluish red.

cue-3,6rdisulfonic acid. 51 fi 1-hygroxy-B-chloronaphthalene-3.6-disu.lfonic Scarlet.

aci 52 6 Methyl 2,4,6-trichlor0-5-carb0yx- 2-hydroxy-6-chl0ronaphthalenc-4-snlionic acid Orange.

pyrimidine. 53 6 Chlorine do l-hydroxynaphthalene-S.8-disulfonic acid Scarlet. 54 2.4.G-trichloro-fi-carboxyl-hydroxynaphthalene-5.7-disulfonic acid Do,

methylpyrimidine. 55 do 1-(4-methyl)-phenyslufonylamino-S-hydroxy- Bluish red.

naphthalene-3.6-disulfonic acid. 56 do 2-benzoylamino-S-hydroxynaphthalene-7- Scarlet.

sulfonic acid. 57 do 2-pr0pionylaminn-S-hydroxynaphthalene-fi- Red.

snlfonic acid. 58 d0. 2-bcnzoylamino fi-hydr0xynaphthalene-6- Red.

sulionic acid.

LS-dihydrcxynaphthalene-B.6-disulionic acid Red.

l-acetcacetylamincbenzene-3-sulfonic acid Yellow. 61 do 1-acefloacetylamino-Z-methylbenzene-4-sulfonic Do.

aci 62 do l-acetcacetylaniinonaphthalene-S-sulfcnic acid-.. Do. 63 6 Bromine do Z-benzoylamino8-hydroxynaphtha1ene35- Red.

disulfonic acid. 64 2.4.5.6te trabr0m0- 2-acetylamino-8-hydroxynaphthalene-3.6- Red.

pyrimidine. disulionic acid. 65 2.4.6{richlo1'0-5-br0mo- 2-acetoacctylaminonaphthalene-4.6.8-trisulfonjc Yellow.

pyrimidine. acid. 66 2.4.fi-trichloropyrimldnlel-acegoacetylamino-4-methylb enzene-fZ-sulfonic D o.

acl 67 do 1-acetoacetylamino-4-chlorobenzene-2-sulfonic Do.

ac 68 2.4.5.6-tetracl1lorol-acetoacetylaminobenzene-2.5-disulfonic acid. Do,

pyrnmdme. 69 do l-acegoacetylaminonaphthalene-4.8-disulionic Do.

aci 70 2.4.5.6-tetrabromo- 1-acetoacetylaminonaphthalene-3.6.8-trisulfonic Do.

pyrimidine. acid. 17 do- 2-hydroxynaphthalene-3.6.8-trisulfonic acid Red.

TABLECcnt: d

Substituents of A Shade of the Paddyeings on Cotton No. of Posi- Substit- Posi- Substit- Z equals radical of D3 equals radical ofor of the Dyeings Example tion uent tion uent on 001 72 2.4.5.G.-tctrabromol-naphthyl-(2')-3 metl1yl-5pyrazolone-6.8- Yellow.

pyrimidine. disulfonie acid. 73 6 Hydroxy 2.4.6-trichlropyrimidine 2-acet1oacetylaminonaphthalene-5,7 disulfonic Do.

aci 74 6 Chloro 2.4.6tribromopyrimidine 2-ace giacetylaminonaphthalene-6.8-disulfonic Do.

acl 75 do l-acetylamino-8-hydroxyuaphthalcne-3.6- Bluish red.

disulfonic acid. 76 2.4.6-trichloropyrimidine 2-propionylamino-5-hydroxy'naphthalene-7- Scarlet.

sulfonic acid. 77 6 Methyl do- 2-ace taylami.uo-8-hydroxynaphthalene-G-sulionic Red.

aoi 72 do. Lacetoacetylaminobenzene-Bsullonic acid Yellow. 79 dol-acetoacetylaminouaphthalene-fi-sulfonic acid Do. 80 2.4.fi-trichloro--methyl- 2-acetylamino-fi-hydroxy-naphthalene-7-sulfonic Scarlet.

p iun'dine. acid. 81 2.4.6-trichloropyrimidine- 2-forrgylamino-5-hydroxynaphthalene-7-sulfonic Do.

801 82 do. l-iormylamino-S-hydroxynaphthalene'3.6- Bluish red.

disulr'onic acid. 83 6 Hydroxy do l-phenyl-3-methyl-5-pyrazolone-3-sulfonic Yellow.

aci 84 6 Methyl .do 1-phenyl-3-methyl-S-pyrazoloneQ-sulfonic acid Do. 85 -do l-acetoacetylamino-Z-methoxyhenzene-5- Do.

sulfonic acid. 86 do l-acetoacetylaminonaphthaleue-7-sulionic acid-.. Do.

87 6 Br l-acetioacetylaminonaphthalene-3.6-disulionic Do.

aci 88 4 Methyl .do. 2-hydroxynaphthalene-6.S-disulfonic acid Orange. 89 4 Chlorine do 2-acet1acetylaminouaphthalene-4.8-disulfonic Yellow.

acl 90 6 Cyano dn 1-(2-chloro) -phenyl-8-mcthyl-5-pyrazclone-5" Do.

sulionic acid. 91 6 .do do lf ylaminonaphthalene-Zi.8-disulfonic Do.

aci Q2 l-aoetoacetylaminonaphthalene-8-sulionic acid.-- Do. 93 2.4.6-trichloro-5carboxy- 2-acetoacetylaminonaphthalcne-esulfonic aci Do.

methylpyrimidine. 94... do 1-acetoacetylamino-2.idimethylbenzene-d Do.

sulfonic acid. 95 n l-acetloacetylaminoachlorobenzene-e-sulfonic Do.

aci 9 2.4.6-tribromo6-carboxy- Z-acetoacetylaminonaphthalene-6.8-disulfonic Do.

methylpyrimidine. aci 97 6 Hydroxy 2.4.6-trichloropyrimidiue l-hydroxynaphthalene-4.6-disulionic acid Scarlet. 98 6 do l-hydI0xynaphthalene-3.fi-dlsull'onic acid... D W do Z-amino-S-hydroxynaphthaleue-G-sulionic aci (acid coupling). 1 no dn 2-amino-8-hydroxynaphthalene-S.fi-disulionic Red.

acid (acid coupling). 1m 2.4.6-trichloropyrimidine-.. 1-hydroxy-7-(4-nitrophenylazo)-8-amino- Greenish black.

naphthalene-B.6.2-trisulfonic acid. 102 do 2-amino-5-hydroxynaphthalene-7-sulfonie acid Red.

(acid coupling). 103 2.4.5.6tetrachloropyrnml-amino-B hydroxynaphthalene-ii.o disulfonic Bluish red.

dine. acid (acid coupling). 4 do l-liydroxy i-phenylazo-S-aminonaphthalene- Dark green;

3.5.4-trisulfonic acid. 105 2.4.6-trichloropyrim1dme do Do. 106 do 1-hydroXY-5phenylazo-fi-aminonaphthalene- Red-brown.

3.4-disu.lfonic acid. 107 2.4.6trichloro-5carboxyn Do.

methylpyrimidine. 108 6 Methyl do 1-hydroxy-7-phenylazo-Saminonaphthalene- Dark green.

3.6.3-trisulfonic acid. 109 2.4. 5.frtetrabromopynmi- .do Do.

1116. 110 2.4.6-tribromopyrimidine. l-amino-8-hydroxynaphthalene-4.fi-disulfonic Bluish red.

acid (acid coupling). in Bordeaux.

The metallizable dyes of Examples 22, 23, 73, 83, 97 and 98 can be treated with metal-yielding agents. If their dyeings are fixed on the fiber, and then aftercoppered, they present the following shades Example No. Shade of aftercoppered dyeing 22 brownish red.

23 do. 73 orange-yellow. 83 do. 97 brownish red. 98 do.

Example 112 2.4.6-trichloropyrimidinel-hydlroxy-8-aminonaphthalenc-5.7-disulionic able by the procedure described in the first paragraph of Example 2, are strewn in and the suspension stirred overnight at 2025, a constant pH value of 5.0-5.5 being maintained by the addition of dilute sodium hydroxide solution. The solution is then rendered weakly alkaline by the addition of sodium hydroxide solution and heated at 4050 for several hours until the remaining sulfonic acid chloride groups are saponified to sulfonic acid groups. The dye is salted out, filtered with suction and dried at 50 with vacuum. A dark blue powder is obtained which gives turquoise colored solutions in water. Mercerized cotton sateen is printed with a paste of the following composition:

15 The printed fabric is dried, steamed for 10 minutes at 100-103", rinsed in cold and then in warm water, soaped at the boil for 15 minutes and rinsed again in warm and cold water. A brilliant turquoise .blue print with very 16 which are produced according to the particulars of Examples 112 and 113, are listed in the following Table 2. They are characterized in Columns (I) to (VIII) by the positions of the SO H and SO groups in the copper good light and Wet fastness is obtained. 5 phthalocyanine molecule, by the values of x and y, by the By condensing copper-phthalocyanlne-trisulfonic acid substituents of the nucleus A and their positions and by chloride-obtained by sulfochlorination of the metal the halopyrimidine from which Z is derived. Since the phthalocyanine for 23 hours at 115-120with 3-aminoshade of the dyeings n Wool or cotton is in each instance 1-(dichloropyrimidyloxymethyl)- or -1-(trichloropyrirniturquoise blue, it has not been mentioned in a separate dyloxymethyl)-benzene (from 2.4.6-trior 2.4.5.6-tetracolumn of the table.

TABLE 2 Example Positions Substit- Posi- Substit- Posi- No. of -SO3H a: y uent tion uent tion Z equals radical ofand -SO2 3 2,4,6-triehloro imidine.

3 CH3 6 0. pyr

1 CH3 6 2,4,6-tricl1loropyrimidine.

1 c1 6 Do.

1 CN 6 D0.

1 Q1130 6 Do.

1 C2H5O 6 2,4,5,6tetrachloropyrimidine.

1 CH3 4 D0.

1 (321150 5 2,4,6-trich1oropyrimidine:

2 CH3 6 D0.

1 CH3 2 DO.

i 2 4 111 b d ,fi-tric oro-5-car oxymeth l rimi ine.

1 OH 4 2,4,6trichloropyrimidine. y Dy 1 OH 4 Br 5 Do.

1 Cl 5 CH3 6 Do.

1 Br 6 Do.

1 2,4,6-trichloro-S-bromopyrimidlne.

1 2,4,6-trichloro-5-methylpyrimidine.

1 l. 2,4,6-tribromopyrimidine.

1 2,4,6-trichloro-5-carboxypyrimldlne.

chloropyrimidine), excellent wool dyes are obtained which can be dyed as described in Example 2. The dyeings possess excellent fastness to wet treatments.

Example 113 53.4 parts of the trisodium salt of copper-phthalocyanine-4,4,4"-trisulfonic acid-4'-sulfonic acid-(3-hydroxymethyl) phenylamide (obtained from copperphthalocyanine-4,4',4",4"-tetrasulfonic acid chloride and 3-hydroxymethyl-l-aminobemene) are dissolved in 700 parts of water at room temperature. After cooling to about 5 the pH value is adjusted to 12.5 with 30% sodium hydroxide solution and 10 parts of 2.4.6-trichloropyrimidine are added in about 1 hour at 5-10". The mixture is stirred for several hours at 5-10", the pH-value being maintained at 1212.5 by means of sodium hydroxide solution. When the condensation is completed the reaction mass is neutralized with hydrochloric acid and the dye is precipitated with sodium chloride, filtered ofi, washed with a sodium chloride solution, dried and ground. It is a blue powder which is soluble in water with a turquoise coloration and dyes cellulose fibers according to the dyeing or printing methods described in Examples 4, 5 and 6 in turquoise shades fast to light and to wet treatments.

Further copper-phthalocyanine dyes of the formula Example 139 54.8 parts of sodium 1-amino-4-(3-hydroxymethylphenylamino) anthraquinone-2.7-disulfonate are dissolved in 350 parts of water in the presence of 17 parts of a 30% sodium hydroxide solution and 0.1 part of an anion active wetting agent. The solution is cooled to 0-2 and under vigorous stirring a solution of 18.4 parts of 2,4,6-trichloropyrimidine in 20 parts of acetone are added dropwise in about 10 minutes. Stirring is continued for further 3 hours at 0-? whereupon the reaction mass is diluted with 500 parts of ice-cold water. The pH-value is adjusted to 6.0-6.3 with acetic acid and the dye is precipitated by addition of sodium chloride, filtered oflf, redissolved in water and re-salted out. It is then filtered off, dried in vacuum at 40 and ground to a blue powder which dissolves in water with a blue coloration.

By replacing the 54.8 parts of sodium 1-amino-4-(3'- hydroxymethyl phenylamino)-anthraquinone-2.7-disulfonate by 44.6 parts of sodium l-amino-4-(3-hydroxymethyl-phenylamino) anthraquinone-Z-sulfonate and carrying out the reaction in dilute aqueous solution (about 1600 parts of water) a less soluble dye is obtained which dyes wool or cotton in blue shades. Applied by a pad-dyeing technique and fixed at 25 in a salt solution containing sodium metasilicate and sodium hydroxide it shows a reactivity many times greater than that showed by the next comparable dye with a -NH bridge instead of the -CH -O- bridge.

The following table contains further anthraquinone dyes which are produced according to the teaching of Example 139 and correspond to the formula 18 2',6'-dimethyl)-phenylamino anthraquinone-Z-sulfonic acid or when in place of 3-amino-1-(dichloropyrimidyloxymethyl)-benzene one of the following condensation products are employed:

)2 50 H (a) 3-aminobenzyl alcohol plus 2,4,5,fi-tetrachloropyrimidine. X 3 (b) B-aminob enzyl alcohol plus 2,4,6-trichloro-5-bromopyrimidine.

(c) 3-aminobenzyl alcohol plus 2,4,6-tribromopyrimidine. (d) dagaaobenzyl alcohol plus 2,4,6tr1chloro-5-carboxymethylpy 0 NH (9) damino--inethyl-benzyl alcohol plus 2,4,6-trichloropyrimidine.

(f) 3-amiuo-4-chlorobenzyl alcohol plus 2,4,6-trichloropyrimidine. (g) 3-amino4-cyanobenzyl slcohol plus 2,4,6-trichloropyrimidine. CH -OZ (h) 3-aIin1i10-4-methoxybeuzyl alcohol plus 2,4,5,6-tetraehloropyr1mi (l) 3-aimiu o4,5-diethoxybenzyl alcohol plus 2,4,6-trichl0ropyriml me. (k) 3arninit r?rmethyl-5-chlorobenzyl alcohol plus 2,4,6-tricl1loropy rum me. j y Charactgnzeq y the substltuent X and Its P (l) 3-amino-2-methylbenzyl alcohol plus 2,4,6-trichloropyrimidine. tron 1n the anthraqumone nucleus (Columns (I) and E 3 g gfifig'gfiggg gg g fi gfi g5& gfgfig i ggggfific y the Substltuents of the nucleus A and then (0) 3amino-6cl1lorobenzyl alcohol plus 2,4,(rtrichloropyrimidina ifi (col (111) t (V1) b th h 1 -1 i (p) Semingfi-methyl-dchlorobenzyl alcohol plus 2,4,6-trichloropy riml 9.

iii if? 3? i i 3 by 2% tzaaatsntrsaslsa las 35a 1' zy c ,,-rc r-- y o e yemgs on WOO or cotton Olumn (s) 3-amino-benzyl alcohol plus 2,4,6trichl0ro-5-carboxypyrlmidme.

TABLE 3 Posl- Substituents of A Shade of tion T P T P Z equals radial of- Dyeing ype 0s. ype os.

(II) (III) (I I 6 2,4,6'trichloropyrlmldine do 5 CH 6 do 7 C1 6 do 5 01130 6 2,4,5,((i)-tetrachloropyrimidine -.IIIIIIIIIIIIIIIIIII1-. -.III'iijs-triiflblb ifiiiifiiififibfiiiidih:IIII Do: 6 0211 0 5 0 11 0 6 2,4,6-trichloropyrimidine- Do. 6 CH 4 d Do. 7 CN 6 Do. 7 CH3 2' C1 D0. 7 011 0 4 Do. 7 2,4,G-triehlorofi-methylpyr1m1dme D0. 6 Cl 5' CH3 2,4,fi-triehloropyrimidine 1130. 0. Do. 2,4,6tribromopyri1m'dine Do. 2,4,6-trichloro-5-bromopyrimidiue Do.

Example 158 43.6 parts of 100% 1-amino-4-(2,4',6'-trimethyl) phenyl-amino-anthraquinone-Z-sulfonic acid are entered in 270 parts of chlorosulfonic acid at 20-30". When everything is dissolved, 80 parts of sulfuryl chloride are dropped in and the temperature increased to 50 in about minutes. After being maintained for 16 hours at -55 the mixture is allowed to cool and then run into a mixture of 2000 parts of ice, 1000 parts of water and 200 parts of sodium chloride. The precipitate is filtered with suction, washed with 10% sodium chloride solution and suspended in 500 parts of water. The suspension is adjusted to pH 7 and 33 parts of finely pulverized 3-amino- 1-(dichloropyrimidyl-oxymethyl)-benzene, obtained by the procedure given in the first paragraph of Example 2, are strewn in. Stirring is continued for a few hours at 20-30 with the addition of dilute sodium carbonate solution to maintain the pH value of the mixture at 7-7.5. When condensation is completed, the mixture is strongly acidified with hydrochloric acid, and the precipitated dye filtered with suction, washed with 1% hydrochloric acid to remove the small excess of 3-amino- 1-(dichloropyrimidyloxymethyl)-benzene. The resulting dye paste is carefully neutralized with sodium carbonate and dried at 50 with vacuum. The ground dye is a dark blue powder which dissolves in water with a blue coloration and dyes wool by the dyeing method of Example 2 in brilliant blue shades of very good fastness to light, washing, milling, water, perspiration, rubbing and dry cleaning. The pad-dyeings and prints on cotton and viscose filament or staple fiber materials also possess very good light and wet fastness properties.

Similarly good dyes are obtained when the starting dye is replaced by 1-amino-4-phenylamino, -4-(2'-,3'- or 4'- methyl, -ethyl or -chloro)-pheny1amino-, 4-(2- or 4- methoxy or -ethoxy)-phenylamino-, 4-(2,4'-, 2',5'- or Example 159 123 parts of 3-aminobenzyl alcohol are added to a solution of 54 parts of anhydrous sodium carbonate in 500 parts of water and in the course of 1 hour 240 parts of 4- acetylamino-benzenesulfonic acid chloride are added to the solution. The temperature is maintained at 3540 until condensation is completed, and the resulting 3-(4'- acetyla'minophenylsulfonylamino)-benzyl alcohol is isolated in the normal manner.

160 parts of dried 3-(4'-acetylaminophenylsufonylamino)-benzyl :alcohol are suspended in 300 parts of Water and 50 parts of 36% hydrochloric acid. The suspension is brought to the boil, held at the boil for 30-60 minutes and neutralized to precipitate the amine formed, which is then salted out, filtered with suction and dried.

27.8 parts of 3-(4'-aminophenylsulfonylamino)-benzyl alcohol are mixed with 350 parts of water, 30 parts of 30% hydrochloric :acid and small amounts of an emulsifying agent. The mixture is cooled to 10, diazotized at 10- 15 by adding a solution of 7 parts of sodium nitrite in 20 parts of Water with vigorous stirring, and stirred at 10-15 for about 1 "hour longer to complete diazotization. The insoluble impurities are filtered off and the clear filtrate run slowly into a solution, cooled to 0, of 45 parts of sodium 1-hydroxy-naphthalene-3,6,8-trisulfonate and 25 parts of sodium carbonate in 450 parts of water. The mixture is stirred for a few hours at 5-10 to complete the coupling reaction.

It is then diluted to 1500 parts and the pH value adjusted to 12 with 30% sodium hydroxyde solution. 20 parts of 2.4.6-trichloropyrimidine are added in small portions over 2 hours at 8-10". The mixture is stirred at 8-10 with the pH value maintained at 11-12 until after 1020 hours the condensation is completed. After neutralization the dye formed is salted out, filtered oif, washed with a sodium chloride solution and dried with vacuum. It is a red 1 9 powder and dyes wool, silk, synthetic polyamide fibers and cellulosic fibers in red shades with very good light and wet fastness properties.

When the diazo component 3-(4'-aminophenylsulfonylamin)-benzyl :alcohol is replaced by the equivalent amount of 3-(3'-aminophenylsufonylamino)-benzyl-alcohol or 3-(4'- or 3'-aminobenzoylamino)-benzyl alcohol, dyestuffs with equally good properties are obtained.

The 3-(4- or 3-aminobenzoylamino)-benzy1 alcohol can be prepared, for example, as follows: A solution of 123 parts of B-aminobenzyl alcohol in 2000 parts of water is mixed with a solution of 300 parts of crystallized sodium acetate in 1000 parts of water. The mixture is held at 2025 and 200 parts of 3- or 4-nitrobenzoyl chloride are slowly added. It is stirred at about 2535 until no further amino group is indicated, upon which the precipitated condensation product is filtered with suction :and the nitro group reduced to the amino group in aqueous or aqueousorganic suspension or in aqueous-organic or organic solution with iron filings and acid by the Bchamp method or by catalysis with hydrogen.

In place of 2.4.6-trichloropyrimidine, 2.4.6-trichloro-5- methyl-, -5-bromo-, -5-carboxyor -5-carboxymethylor 2.4.5.6 tetrachloropyrimidine, or the corresponding bromopyrimidines can be used for the condensation with the hydroxymethyl group of the dye.

The 3-aminobenzyl alcohol can be replaced by any one of its derivatives bearing a methyl, methoxy or cyano group or a chlorine or bromine atom in the position 4 or a methyl or methoxy group in the 6 position or a methyl group in the position 2 and a chlorine atom in the position 5.

Instead of sodium l-hydroxynaphthalene-3.6.8-trisulfonate other coupling components such as those mentioned in the Examples 1 to 111 can be employed, preference being given to the coupling components with two to three sulfonic acid groups which render the final dye sufficiently soluble in the printing pastes and in the padding liquors, whereas the dyes produced from coupling components with one sulfonic acid group are suitable for the conventional dyeing methods using dyebaths in which the dye concentration is very small.

Especially valuable dyes for printing and pad-dyeing cotton are obtained by employing the same halopyrimidines and the same coupling components as in the Examples 2 (fourth paragraph) 3, 4, 5, 8, 12, 20, 26, 27, 28, 33, 38, 42, 43, 54, 64, 65, 75, 101 and 108.

Example 160 68.7 parts of the monoazo dye (as the disodium salt) produce by coupling diazotized 2-amino-naphthalene-4,8- disulfonic :acid with 2-hyroxynaphthalene-6-sulfonic acid- (3'-hydroxymethyl)-phenylamide in strongly alkaline solution are dissolved in 1000 parts of water. The solution is cooled to 810 and the pH value brought to 11-12. In the course of 2 hours 20 parts of 2.4.6-trichloro-pyrimidine are added in small portions with vigorous stirring and stirring is then continued at 810 until the condensation is completed, which takes from 10 to hours. During this time the pH is maintained at 11-12. After neutralization of the solution, the dye formed is salted out, filtered off, washed with common salt solution and dried. It is a water-soluble red powder and dyes wool, silk, synthetic polyamide and cellulose fibers in brilliant red shades of very good light and wet fastness.

The coupling component is produed as follows: 382 parts of the benzene-sulfonic acid ester of 2-hydroxynaphthalene-d-sulfonic acid chloride (prepared according to German Patent 859,027) are added in small portions with good stirring to a mixture at 40-50 of 123 parts of 3- aminobenzyl alcohol, 200 parts of crystallized sodium acetate and 1500 parts of Water. The whole is stirred at 40- 50 until condensation is completed. On cooling, the precipitate is filtered with suction, stirred into 3500 parts of 4% sodium hydroxide solution and the mixture heated until saponification of the benzenesulfonic acid ester is completed. The 2-hydroxy-naphthalene-6-sulfonic acid- (3 hydroxymethyl)-phenylamide thus formed is precipitated by acidifying the solution, and then filtered with suction, washed and dried.

The 2.4.6-trichloropyrimidine can be replaced by one of the halopyrimidines mentioned in Example 159.

Instead of the 2-aminonaphthalene-4.8-disu1f0nic acid employed in the production of the starting dye, other diazo components with at least one, and preferably two or three, sulfonic acid group e.g. 1-aminobenzene-2.4- or -2.5-disulfonic acid, 1-aminonaphthalene-3.6-, -3.8 or -4.8-disulfonic acid, 1-aminonaphthalene-3.6.8-trisulfonic acid, 2- aminonaphthalene-3.6-, -5.7- or -6.8-disulfonic acid, 2- amino-naptha1ene-3.6.8- or -4.6.8-trisulfonic acid or 4- amino-l.1'-azobenzene-4.3-disulfonic acid can be employed.

By replacing the 3-aminobenzyl alcohol by one of its derivatives mentioned in Example 159 or the benzenesulfonic acid ester of 2-hydroxynaphthalene-6-sulfonic acid chloride by a benzene-, methylbenzeneor methanesulfonic acid ester of another 1- or 2-hydroxynaphthalenesulfonic acid chloride similar coupling components are produced.

Formulae of representative dyes of the foregoing examples are as follows:

Examples 1 and 2 Example 3 on NH-COO Example 4 I ml I-IC \N H I OCHz HOaS SOaH 01-0 0-- Example 5 SOaH all T 0 (1H o1o 2 SOSH N SOaH Example 7 01 OH I The groups SO H and -SO; are in the positions O 3,3,3,3' of the copper phthalocyanine radical.

SOaH H-C N 5 Example 113 con'esponds to the same general formula C14") I|I 0- H: as Example 112, but the groups SO H and -SO are y J in the positions 4,4,4",4 of the copper phthalocya- N SOSH nine radical.

Example 17 OH I OH:

I xampe I I -OCH: $03K 01- ol N SO H 0 NH:

II I H038 SOZH Example 18 OH: OH

I (I two a lo} (ll- 2 N- N C-H CHz-O I II I -0CH: 11038 C\ C-Cl CIC\ /C- i \N/ N/ V S0311 Example 139 (last paragraph) 0 NH: Example 19 I I.i)H SOaH all C 131-0 N H I I I I -O-CH: 1103s 0 NH (3 -01 01- o-J N C-H N 80:11 CH20 A II L- /o-o1 O NH: I I Example 158 I "I CH3 /SOr-NH 0\ --C1 I (I) N C-H O NH CH3 H'.*O- I II 0 0-01 CH: N

Example 101 OH NH: 803K 3,418,308 23 24 Example 159 CH s og]; (ll- NHzS-C N=N HC N H O-CH2 HOsS SOaH 01-0 0- Example 160 OH I hydrogen, hydroxy, chlorine, bromine, cyano, methyl and lower alkoxy,

N=N R is a member selected from the group consisting of hydrogen, chlorine, bromine, methyl and lower alkoxy,

| '1 R is a member selected from the group consisting of S030 SOHIH Cl hydrogen, chlorine, bromine, methyl, carboxy and C-H carboxymethyl, CH2O-' IL 01 hal is a halogen atom with an atomic number from 17 L to 35, inclusive,

n is one of the integers 1 and 2, and Having thus disclosed the invention what we claim is: m i one of the integers 1 and 2-, 1. Water-soluble dyes of the formula 2 2- m I C C he].

wherein D is the radical of a dye selected from the group 2. Water-soluble dyes of the formula consisting of (a) a benzene-azo-naphthalene dye, a benzene-azo-S- pyrazolone dye and a naphthalene-azo-naphthalene l dye, the said monoazo dyes bearing from 1 to 3 sulfonic acid groups, N fi (b) a 1-amino-4-phenylamino-anthraquinone-Z-sulfonic J C-hal acid dye, a 1 amino-4-phenylamino-anthraquinone-Z,S-disulfonic acid dye, wherein D 1s the radical of a couphng component beara 1- amino-4-pheny lamino-anthraquinone-Z,6-disulfonic mg from 1 to 3 slflffmlc 'acld groups and selected acid dye, from the group conslstlng of the hydroxynaphthalene, a 1 amino-4-phenylamino-anthraquinone-2,7-disulf0nic ammo'naphthalene, 'P Y Y 'PY acid dye, 1-naphthyl-3-methyl-5-pyrazolone, acetoacetylammoa 1 amino-4-phenylamino-anthraquinone-2,8-disulfonic benfzene acetoacetylammophthalene and p y acid dye and annno-hydroxyn-aphthalene, phenylazo being in ortho- (c) a copper-phthalocyanine dye bearing from 2 to 3 PPSmOB to ammo,

water-solubilizing groups selected from the group con- 2 15 a member sflected q the group conslstmg of i ti of SO3H and hydrogen, chlorine, bromme, methyl and lower alk- D is a radical selected from the group consisting of 3;

1-amino-2-sulfo-anthraquinonyl-4, 1-amino-2,5-disul- 3 15 a member 9 the g p coflslstlng of fo-anthraquinonyl 4, 1-amino-2,fi-disulfo-anthraquihydrogen, chlolme, bl'omlne, methyl, carboxy and nonyl-4, 1-amino-2,7-disulfo-anthraquinonyl-4 and 1- cafboxymethyl, and i 2 8 di 1f th i 1 4 hal 15 a halogematom with an atomic number from D is the radical of a coupling component bearing 1 17 to 35, lncluslveto 3 sulfonic acid groups and selected from the group water'soluble dyes of the formula consisting of the hydroxynaphthalene, amino-naphthalene, 1-phenyl-3-methyl-5-pyrazolone, l-naphthyll 3 methyl 5-pyrazolone,acetoacetylaminobenzene,

acetoacetylaminonaphthalene and phenylazo-amino- T I hydroxynaphthalene, phenylazo being in ortho-posi- TSOPNH c hal tion to amino, N Q is a member selected from the group consisting of CO and SO and is bound to a carbon atom I- Of D1, R is a member selected from the group consisting of wherein R is a member selected from the group consisting of hydrogen, chlorine, bromine, methyl and 8. The dye of the formula lower alkoxy,

OH 011 R is a member selected from the group consisting of a hydrogen, chlorine, bromine, methyl, carboxy and L NZN carboxymethyl, hal is a halogen atom with an atomic number from 17 H C N H038 to 35, inclusive, and 0 p is one of the integers 1, 2 and 3. 80311 4. Water-soluble dyes of the formula 9. The dye of the formula on ml 5 1 It I -0-oH1 11038 01- o- 10. The dye of the formula 0H NH-G 00 wherein 2 is a member selected from the group consist- I mg of hydrogen, chlorine, bromine, methyl and lower alkoxy H C --OCH HO 5 so H R, is a member selected from the group consisting of (11-9 Bi-l a 3 hydrogen, chlorine, bromine, methyl, carboxy and carboxymethyl,

hal is a halogen atom with an atomic number from 17 to 35, inclusive, and

r is one of the integers 1 and 2. The dye of the formula 5. The dye of the formula 01 H? C-N SO H OH I- I l a Cl C N=N-C r l Cl N N HC N C=N H C N 40 c1 (2 O CH' (H13 0- H o o1-r'i d-- C a S N .l

12. The dye of the formula 6. The dye of the formula HO N 01- N=N-C I S OH 01-: N=N \N 3 H I 0CH: l H O N 01-0 C- CH;

II I -0CH: 0, J o1-o c- N N 3031 13. The dye of the formula 0H NH: S|O1H 01 ('3 N=N N=N -N0:

HC/ N H l "0CH| H035 S0aH c1-o ol N/ 7. The dye of the formula 14. The dye of the formula -(SOaH);

CuPC (I: 1 Cl C\ N=N TSOr-NH -Cl H-o N I N/ 0-11 I I OCH: HOaS SOsH CHr-O I ll 01- cc 0-01 J l 27 28 wherein the groups SO H and SO are in the 17. The dye of the formula positions 3,3,3",3"', of the copper phthalocyanine radical. O NH:

15. The dye of the formula I 0 11 -(SOaH): S a v v I 01101 Q 1 I -S0=NH c lcl CH; SOnN-H 0 -01 l N 0-H l l N C-H CH:O I II 0 NH CH3 CH:-O- l H l-o o-01 L-o c-c1 \N CH3 \N wherein the groups -SO H and SO are in the positions 4,4,4",4"' of the copper phthalocyam'ne molecule.

16. The dye of the formula References NH, UNITED STATES PATENTS I 3,218,310 11/1965 Benz et a1. 260154 CHARLES B. PARKER, Primary Examiner. D. M. PAFUGA, Assistant Examiner.

I u O NH C -C1 Q V US. Cl. X.R.

N C-H 

